US7041239B2ExpiredUtilityPatentIndex 97
Electrodes comprising mixed active particles
Est. expiryApr 3, 2023(expired)· nominal 20-yr term from priority
H01M 4/505H01M 4/5825H01M 4/525H01M 4/582H01M 4/364H01M 4/13H01M 10/0525H01M 4/587H01M 10/052Y02E60/10
97
PatentIndex Score
73
Cited by
42
References
165
Claims
Abstract
Electrode active materials comprising two or more groups of particles having differing chemical compositions, wherein each group of particles comprises a material selected from: (a) materials of the formula A 1 a M 1 b (XY 4 ) c Z d ; and (b) materials of the formula A 2 e M 2 f O g ; and wherein (i) A 1 , A 2 , and A 3 are Li, Na, or K; (ii) M 1 and M 3 comprise a transition metal; (iv) XY 4 a phosphate or similar moiety; and (v) Z is OH, or halogen. In a preferred embodiment, A 2 e M 3 f O g is A 3 h Mn i O 4 having an inner and an outer region, wherein the inner region comprises a cubic spinel manganese oxide, and the outer region comprises a manganese oxide enriched in Mn +4 relative to the inner region. In a preferred embodiment, the compositions also comprise a basic compound.
Claims
exact text as granted — not AI-modified1. An electrode active material comprising two or more groups of particles having differing chemical compositions, wherein each group of particles comprises a material selected from:
(a) materials of the formula A 1 a M 1 b (XY 4 ) c Z d ;
(b) materials of the formula A 2 e M 2 f O g ; and
(c) materials of the formula A 3 h Mn i O 4 ;
wherein
(i) A 1 , A 2 , and A 3 are independently selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a≦8, 0<e≦6, and h≦2.0;
(ii) M 1 is one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 0.8≦b≦3;
(iii) M 2 is one or more metals, comprising at least one metal selected from the group consisting of Fe, Co, Ni, Mo, V, Zr, Ti, Mo, and Cr, and 1≦f≦6;
(iv) XY 4 is selected from the group consisting of X′O 4−x Y′ x , X′O 4−y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; X″ is selected from the group consisting of P, As, Sb, Si, Ge, V and mixtures thereof; Y′ is halogen; 0≦x<3; and 0<y<2; and 0<c≦3;
(v) Z is OH, halogen, or mixtures thereof, and 0≦d≦6; and
(vi) 0<g≦15;
(vii) M 1 , M 2 , X, Y, Z, a, b, c, d, e, f, g, h, i, x and y are selected so as to maintain electroneutrality of said compound; and
(viii) said material of the formula A 3 h Mn i O 4 has an inner and an outer region, wherein the inner region comprises a cubic spinel manganese oxide, and the outer region comprises a manganese oxide that is enriched in Mn +4 relative to the inner region;
wherein the electrode active material comprises a material of the formula A 1 a M 1 b (XY 4 ) c Z d , wherein XY 4 is PO 4−x F x , and 0<x≦0.2.
2. An electrode active material of claim 1 , wherein said material of the formula A 1 a M 1 b (XY 4 ) c Z d has an olivine structure.
3. An electrode active material of claim 1 , wherein said material of the formula A 1 a M 1 b (XY 4 ) c Z d has a NASICON structure.
4. An electrode active material according to claim 1 , wherein A 1 comprises Li.
5. An electrode active material according to claim 1 , wherein M 1 comprises at least one element from Groups 4 to 11 of the Periodic Table; and at least one element from Groups 2, 3, and 12–16 of the Periodic Table.
6. An electrode active material according to claim 5 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, Mo and mixtures thereof.
7. An electrode active material according to claim 6 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Mn, Ti, and mixtures thereof.
8. An electrode active material according to claim 5 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.
9. An electrode active material according to claim 8 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Al, and mixtures thereof.
10. An electrode active material according to claim 1 , wherein Z comprises F, and 0.1<d≦4.
11. An electrode active material according to claim 1 , comprising a material of the formula A 2 e M 2 f O g .
12. An electrode active material according to claim 11 , wherein A 2 comprises Li.
13. An electrode active material according to claim 11 , wherein M 2 is M 4 k M 5 m M 6 n , wherein M 4 is a transition metal selected from the group consisting of Fe, Co, Ni, Mo, V, Zr, Ti, Cr, and mixtures thereof; M 5 is one or more transition metal from Groups 4 to 11 of the Periodic Table; M 6 is at least one metal selected from Group 2, 12, 13, or 14 of the Periodic Table; and k+m+n=f.
14. An electrode active material according to claim 13 , wherein M 4 is selected from the group consisting of Co, Ni, Mo, V, Ti and mixtures thereof.
15. An electrode active material according to claim 14 , wherein M 6 is selected from the group consisting of Mg, Ca, Al, and mixtures thereof, and n>0.
16. An electrode active material according to claim 14 , comprising a material of the formula LiNi r Co s M 6 t O 2 , wherein 0<(r+s)≦1, and 0≦t<1.
17. An electrode active material according to claim 13 , comprising a material selected from the group consisting of LiNiO 2 , LiCoO 2 , γ-LiV 2 O 5 and mixtures thereof.
18. An electrode active material comprising two or more groups of particles having differing chemical compositions, wherein
(a) the first group of particles comprises a material of the formula A 1 a M 1 b (XY 4 ) c Z d ; and
(b) the second group of particles comprises a material selected from materials of the formula A 1 a M 1 b (XY 4 ) c Z d ; materials of the formula A 2 e M 3 f O g ; and mixtures thereof;
wherein
(i) A 1 and A 2 are independently selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a≦8, and 0<e≦6;
(ii) M 1 and M 3 are, independently, one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 0.8≦b≦3, and 1≦f≦6;
(iii) XY 4 is selected from the group consisting of X′O 4−x Y′ x , X′O 4−y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; X″ is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof; Y′ is halogen; 0≦x<3; and 0<y<2; and 0<c≦3;
(iv) Z is OH, halogen, or mixtures thereof, and 0≦d≦6;
(v) 0<g≦15; and
(vi) wherein M 1 , M 3 , X, Y, Z, a, b, c, d, e, f, g, x and y are selected so as to maintain electroneutrality of said compound;
wherein XY 4 of at least one of the first and second group of particles is PO 4−x F x , and 0<x≦0.2.
19. An electrode active material of claim 18 , comprising a material of the formula A a M b (XY 4 ) c Z d having an olivine structure.
20. An electrode active material of claim 19 , comprising a material of the formula A a M b (XY 4 ) c Z d having a NASICON structure.
21. An electrode active material according to claim 18 , wherein A 1 comprises Li.
22. An electrode active material according to claim 18 , wherein M 1 comprises at least one element from Groups 4 to 11 of the Periodic Table, and at least one element from Groups 2, 3, and 12–16 of the Periodic Table.
23. An electrode active material according to claim 22 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.
24. An electrode active material according to claim 23 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Mn, Ti, and mixtures thereof.
25. An electrode active material according to claim 22 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.
26. An electrode active material according to claim 25 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Al, and mixtures thereof.
27. An electrode active material according to claim 18 , wherein X′ comprises Si or a mixture of Si and P, and X″ comprises Si or a mixture of Si and P.
28. An electrode active material according to claim 18 , wherein XY 4 is selected from the group consisting of X′O 4−x Y′ x , X′O 4−y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is P and X″ is P; and 0<x<3; and 0<y<2.
29. An electrode active material according to claim 18 , wherein Z comprises F, and 0.1<d≦4.
30. An electrode active material according to claim 18 , comprising particles comprising a material of the formula A 2 e M 3 f O g .
31. An electrode active material according to claim 30 , wherein 2 comprises Li.
32. An electrode active material according to claim 30 , wherein M 3 is M 4 k M 5 m M 6 n , wherein M 4 is a transition metal selected from the group consisting of Fe, Co, Ni, Cu, Mo, V, Zr, Ti, Cr, and mixtures thereof; M 5 is one or more transition metal from Groups 4 to 11 of the Periodic Table; M 6 is at least one metal selected from Group 2, 12, 13, or 14 of the Periodic Table; and k+m+n=f.
33. An electrode active material according to claim 32 , wherein M 4 is selected from the group consisting of Co, Ni, Mo, V, Ti, Cu and mixtures thereof.
34. An electrode active material according to claim 32 , wherein M 6 is selected from the group consisting of Mg, Ca, Al, and mixtures thereof, and n>0.
35. An electrode active material according to claim 32 , comprising a material of the formula LiNi r Co s M 6 t O 2 , wherein 0<(r+s)≦1, and 0≦t<1.
36. An electrode active material according to claim 30 , comprising a material selected from the group consisting of LiNiO 2 , LiCoO 2 , γ-LiV 2 O 5 , Li 2 CuO 2 and mixtures thereof.
37. An electrode active material according to claim 30 comprising a material of the formula A 3 h Mn i O 4 having an inner and an outer region, wherein the inner region comprises a cubic spinel manganese oxide, and the outer region comprises a cubic spinel manganese oxide that is enriched in Mn +4 relative to the inner region.
38. An electrode active material according to claim 37 , wherein said cubic spinel manganese oxide is Li 1+p Mn 2−p O 4 where 0≦p<0.2.
39. An electrode active material according to claim 18 , additionally comprising a basic compound.
40. An electrode active material according to claim 39 , wherein said basic compound is selected from the group consisting of basic amines, salts of organic acids, and mixtures thereof.
41. An electrode active material according to claim 40 wherein said basic compound is selected from the group consisting of carbonates, metal oxides, hydroxides, phosphates, hydrogen phosphates, dihydrogen phosphates, silicates, aluminates, borates bicarbonates, and mixtures thereof.
42. An electrode active material according to claim 41 , wherein the basic compound is selected from the group consisting of LiOH, Li 2 O, LiAlO 2 , Li 2 SiO 3 , Li 2 CO 3 , Na 2 CO 3 , and CaCO 3 .
43. An electrode active material according to claim 18 , comprising a material of the formula
Li a Co u Fe v M 13 w M 14 aa M 15 bb XY 4
wherein
(i) 0<a≦2, u>0, and v>0;
(ii) M 13 is one or more transition metals, where w≧0;
(iii) M 14 is one or more +2 oxidation state non-transition metals, where aa≧0;
(iv) M 15 is one or more +3 oxidation state non-transition metals, where bb≧0;
(v) XY 4 is PO 4−x F x , and 0<x≦0.2; and
(vi) wherein (u+v+w+aa+bb)<2, and M 13 , M 14 , M 15 , XY 4 , a, u, v, w, aa, bb, x, and y are selected so as to maintain electroneutrality of said compound.
44. An electrode active material according to claim 43 , wherein 0.8≦(u+v+w+aa+bb)≦1.2.
45. An electrode active material according to claim 44 , wherein u≧0.5.
46. An electrode active material according to claim 44 , wherein 0.01<v≦0.5.
47. An electrode active material according to claim 44 , wherein 0.01≦w≦0.5.
48. An electrode active material according to claim 44 , wherein M 13 is selected from the group consisting of Ti, V, Cr, Mn, Ni, Cu and mixtures thereof.
49. An electrode active material according to claim 48 , wherein M 13 is selected from the group consisting of Mn, Ti, and mixtures thereof.
50. An electrode active material according to claim 44 , wherein 0.01≦(aa+bb)≦0.5.
51. An electrode active material according to claim 50 , wherein 0.01≦aa≦0.2.
52. An electrode active material according to claim 51 , wherein M 14 is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.
53. An electrode active material according to claim 52 , wherein M 14 is Mg.
54. An electrode active material according to claim 44 , wherein 0.01≦bb≦0.2.
55. An electrode active material according to claim 54 , wherein M 15 is selected from the group consisting of B, Al, Ga, In and mixtures thereof.
56. An electrode active material according to claim 55 , wherein M 15 is Al.
57. An electrode active material according to claim 44 , wherein u≧0.8, and 0.05≦v≦0.15.
58. An electrode active material according to claim 57 , wherein 0.01≦aa≦0.1.
59. An electrode active material according to claim 57 , wherein M 14 is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.
60. An electrode active material according to claim 57 , wherein 0.01≦bb≦0.1.
61. An electrode active material according to claim 60 , wherein M 15 is Al.
62. An electrode active material according to claim 43 , wherein 0.01≦x≦0.05.
63. An electrode active material according to claim 62 , wherein e≧0.8, and 0.05≦f≦0.15.
64. An electrode active material according to claim 43 , wherein 0.01≦aa≦0.1, and M 14 is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures thereof.
65. An electrode active material according to claim 43 , wherein 0.01≦bb≦0.1, and M 15 is Al.
66. An electrode active material comprising two or more groups of particles having differing chemical compositions, wherein
(a) the first group of particles having an inner and an outer region, wherein the inner region comprises a cubic spinel manganese oxide, and the outer region comprises a manganese oxide that is enriched in Mn +4 relative to the inner region, and
(b) the second group of particles comprises a material selected from materials of the formula A 1 a M 1 b (XY 4 ) c Z d ; materials of the formula A 2 e M 3 f O g ; and mixtures thereof;
wherein
(i) A 1 , A 2 , and A 3 are independently selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a≦8, 0<e≦6;
(ii) M 1 and M 3 are, independently, one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 0.8≦b≦3, and 1≦f≦6;
(iii) XY 4 is selected from the group consisting of X′O 4−x Y′ x , X′O 4−y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; X″ is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof; Y′ is halogen; 0≦x<3; and 0<y<2; and 0<c≦3;
(iv) Z is OH, halogen, or mixtures thereof, and 0≦d≦6;
(v) 0<g≦15; and
(vi) wherein M 1 , M 3 , X, Y, Z, a, b, c, d, e, f, g, x and y are selected so as to maintain electroneutrality of said compound.
67. An electrode active material according to claim 66 comprising a material of the formula A 1 a M 1 b (XY 4 ) c Z d .
68. An electrode active material of claim 67 , wherein said material of the formula A 1 a M 1 b (XY 4 ) c Z d has an olivine structure.
69. An electrode active material of claim 67 wherein said material of the formula A 1 a M 1 b (XY 4 ) c Z d has a NASICON structure.
70. An electrode active material according to claim 67 wherein A 1 comprises Li.
71. An electrode active material according to claim 68 wherein M 1 comprises at least one transition metal from Groups 4 to 11 of the Periodic Table; and at least one metal from Groups 2, 3, and 12–16 of the Periodic Table.
72. An electrode active material according to claim 71 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.
73. An electrode active material according to claim 72 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Mn, Ti, and mixtures thereof.
74. An electrode active material according to claim 72 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.
75. An electrode active material according to claim 74 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Al, and mixtures thereof.
76. An electrode active material according to claim 67 , wherein X′ comprises Si or a mixture of Si and P, and X″ comprises Si or a mixture of Si and P.
77. An electrode active material according to claim 67 , wherein XY 4 is selected from the group consisting of X′O 4−x Y′ x , X′O 4−y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is P and X″ is P; and 0<x<2; and 0<y<4.
78. An electrode active material according to claim 77 , wherein XY 4 is PO 4−x F x , and 0<x≦0.2.
79. An electrode active material according to claim 67 , wherein Z comprises F, and 0.1<d≦4.
80. An electrode active material according to claim 66 , comprising an active material of the formula A 2 e M 3 f O g .
81. An electrode active material according to claim 80 , wherein A 2 comprises Li.
82. An electrode active material according to claim 80 , wherein M 3 is M 4 k M 5 m M 6 n , wherein M 4 is a transition metal selected from the group consisting of Fe, Co, Ni, Mo, Cu, V, Zr, Ti, Cr, and mixtures thereof; M 5 is one or more transition metal from Groups 4 to 11 of the Periodic Table; M 6 is at least one metal selected from Group 2, 12, 13, or 14 of the Periodic Table; and k+m+n=f.
83. An electrode active material according to claim 82 , wherein M 4 is selected from the group consisting of Co, Ni, Mo, V, Ti and mixtures thereof.
84. An electrode active material according to claim 82 , wherein M 6 is selected from the group consisting of Mg, Ca, Al, and mixtures thereof, and n>0.
85. An electrode active material according to claim 82 , comprising a material of the formula LiNi r Co s M 6 t O 2 , wherein 0<(r+s)≦1, and 0≦t<1.
86. An electrode active material according to claim 82 comprising a material selected from the group consisting of LiNiO 2 , LiCoO 2 , γ-LiV 2 O 5 , Li 2 CuO 2 , and mixtures thereof.
87. An electrode active material according to claim 66 , wherein said cubic spinel manganese oxide is represented by the formula Li 1+x Mn 2−x O 4 where x is greater than or equal to 0 and less than 0.2.
88. An electrode active material according to claim 66 , additionally comprising a basic compound.
89. An electrode active material according to claim 88 , wherein said basic compound is selected from the group consisting of basic amines, salts of organic acids, and mixtures thereof.
90. An electrode active material according to claim 89 , wherein said basic compound is selected from the group consisting of carbonates, metal oxides, hydroxides, phosphates, hydrogen phosphates, dihydrogen phosphates, silicates, aluminates, borates bicarbonates, and mixtures thereof.
91. An electrode active material according to claim 90 , wherein the basic compound is selected from the group consisting of LiOH, Li 2 O, LiAlO 2 , Li 2 SiO 3 , Li 2 CO 3 , Na 2 CO 3 , and CaCO 3 .
92. An electrode active material comprising two or more groups of particles having differing chemical compositions, wherein each group of particles comprises a material selected from:
(a) materials of the formula A 1 a M 1 b (XY 4 ) c Z d ;
(b) materials of the formula A 2 e M 2 f O g ; and
(c) materials of the formula A 3 h Mn i O 4 ;
wherein
(i) A 1 , A 2 , and A 3 are independently selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a≦8, 0<e≦6, and h≦2.0;
(ii) M 1 is one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 0.8≦b≦3;
(iii) M 2 is one or more metals, comprising at least one metal selected from the group consisting of Fe, Co, Ni, Mo, V, Zr, Ti, Mo, and Cr, and 1≦f≦6;
(iv) XY 4 is selected from the group consisting of X′O 4−x Y′ x , X′O 4−y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; X″ is selected from the group consisting of P, As, Sb, Si, Ge, V and mixtures thereof; Y′ is halogen; 0≦x<3; and 0<y<2; and 0<c≦3;
(v) Z is OH, halogen, or mixtures thereof, and 0≦d≦6; and
(vi) 0<g≦15; and
(vii) M 1 , M 2 , X, Y, Z, a, b, c, d, e, f, g, h, i, x and y are selected so as to maintain electroneutrality of said compound;
wherein the electrode active material comprises a material of the formula A 3 h Mn i O 4 having an inner and an outer region, wherein the inner region comprises a cubic spinel manganese oxide, and the outer region comprises a manganese oxide that is enriched in Mn +4 relative to the inner region.
93. An electrode active material according to claim 92 , wherein said cubic spinel manganese oxide is Li 1+p Mn 2−p O 4 where 0≦p<0.2.
94. An electrode active material according to claim 92 , additionally comprising a basic compound.
95. An electrode active material according to claim 94 , wherein said basic compound is selected from the group consisting of basic amines, salts of organic acids, and mixtures thereof.
96. An electrode active material according to claim 94 , wherein said basic compound is selected from the group consisting of carbonates, metal oxides, hydroxides, phosphates, hydrogen phosphates, dihydrogen phosphates, silicates, aluminates, borates bicarbonates, and mixtures thereof.
97. An electrode active material according to claim 94 , wherein the basic compound is selected from the group consisting of LiOH, Li 2 O, LiAlO 2 , Li 2 SiO 3 , Li 2 CO 3 , Na 2 CO 3 , and CaCO 3 .
98. An electrode active material comprising two or more groups of particles having differing chemical compositions, wherein
(a) the first group of particles comprises a material of the formula A 1 a M 1 b (XY 4 ) c Z d ; and
(b) the second group of particles comprises a material selected from materials of the formula A 1 a M 1 b (XY 4 ) c Z d ; materials of the formula A e M 3 f O g ; and mixtures thereof;
wherein
(i) A 1 and A 2 are independently selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a≦8, and 0<e≦6;
(ii) M 1 and M 3 are, independently, one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 0.8≦b≦3, and 1≦f≦6;
(iii) XY 4 is selected from the group consisting of X′O 4−x Y′ x , X′O 4−y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; X″ is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof; Y′ is halogen; 0≦x<3; and 0<y<2; and 0<c≦3;
(iv) for at least one of the first and second groups of particles, Z comprises F, and 0.1<d≦4;
(v) 0<g≦15; and
(vi) wherein M 1 , M 3 , X, Y, Z, a, b, c, d, e, f, g, x and y are selected so as to maintain electroneutrality of said compound.
99. An electrode active material of claim 98 , comprising a material of the formula A a M b (XY 4 ) c Z d having an olivine structure.
100. An electrode active material of claim 99 , comprising a material of the formula A a M b (XY 4 ) c Z d having a NASICON structure.
101. An electrode active material according to claim 98 , wherein A 1 comprises Li.
102. An electrode active material according to claim 98 , wherein M 1 comprises at least one element from Groups 4 to 11 of the Periodic Table, and at least one element from Groups 2, 3, and 12–16 of the Periodic Table.
103. An electrode active material according to claim 102 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.
104. An electrode active material according to claim 103 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Mn, Ti, and mixtures thereof.
105. An electrode active material according to claim 102 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.
106. An electrode active material according to claim 105 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Al, and mixtures thereof.
107. An electrode active material according to claim 98 , wherein X′comprises Si or a mixture of Si and P, and X″ comprises Si or a mixture of Si and P.
108. An electrode active material according to claim 98 , wherein XY 4 is selected from the group consisting of X′O 4−x Y′ x , X′O 4−y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is P and X″ is P; and 0<x<3; and 0<y<2.
109. An electrode active material according to claim 108 , wherein XY 4 is PO 4−x F x , and 0<x≦0.2.
110. An electrode active material according to claim 98 , comprising particles comprising a material of the formula A 2 e M 3 f O g .
111. An electrode active material according to claim 110 , wherein A 2 comprises Li.
112. An electrode active material according to claim 110 , wherein M 3 is M 4 k M 5 m M 6 n , wherein M 4 is a transition metal selected from the group consisting of Fe, Co, Ni, Cu, Mo, V, Zr, Ti, Cr, and mixtures thereof; M 5 is one or more transition metal from Groups 4 to 11 of the Periodic Table; M 6 is at least one metal selected from Group 2, 12, 13, or 14 of the Periodic Table; and k+m+n=f.
113. An electrode active material according to claim 112 , wherein M 4 is selected from the group consisting of Co, Ni, Mo, V, Ti, Cu and mixtures thereof.
114. An electrode active material according to claim 112 , wherein M 6 is selected from the group consisting of Mg, Ca, Al, and mixtures thereof, and n>0.
115. An electrode active material according to claim 110 , comprising a material of the formula LiNi r Co s M 6 t O 2 , wherein 0<(r+s)≦1, and 0≦t<1.
116. An electrode active material according to claim 110 , comprising a material selected from the group consisting of LiNiO 2 , LiCoO 2 , γ-LiV 2 O 5 , Li 2 CuO 2 and mixtures thereof.
117. An electrode active material according to claim 110 , comprising a material of the formula A 3 h Mn i O 4 having an inner and an outer region, wherein the inner region comprises a cubic spinel manganese oxide, and the outer region comprises a cubic spinel manganese oxide that is enriched in Mn +4 relative to the inner region.
118. An electrode active material according to claim 117 , wherein said cubic spinel manganese oxide is Li 1+p Mn 2−p O 4 where 0≦p<0.2.
119. An electrode active material according to claim 98 , additionally comprising a basic compound.
120. An electrode active material according to claim 119 , wherein said basic compound is selected from the group consisting of basic amines, salts of organic acids, and mixtures thereof.
121. An electrode active material according to claim 120 wherein said basic compound is selected from the group consisting of carbonates, metal oxides, hydroxides, phosphates, hydrogen phosphates, dihydrogen phosphates, silicates, aluminates, borates bicarbonates, and mixtures thereof.
122. An electrode active material according to claim 119 , wherein the basic compound is selected from the group consisting of LiOH, Li 2 O, LiAlO 2 , Li 2 SiO 3 , Li 2 CO 3 , Na 2 CO 3 , and CaCO 3 .
123. An electrode active material comprising two or more groups of particles having differing chemical compositions, wherein
(a) the first group of particles comprises a material of the formula A 1 a M 1 b (XY 4 ) c Z d ; and
(b) the second group of particles comprises a material of the formula A 3 h Mn i O 4 having an inner and an outer region, wherein the inner region comprises a cubic spinel manganese oxide, and the outer region comprises a manganese oxide that is enriched in Mn +4 relative to the inner region;
wherein
(i) A 1 and A 3 are independently selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a≦8, and 0<e≦6;
(ii) M 1 and M 3 are, independently, one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 0.8≦b≦3, and 1≦f≦6;
(iii) XY 4 is selected from the group consisting of X′O 4−x Y′ x , X′O 4−y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is selected from the group consisting of P, As, Sb, Si, Ge, V, S, and mixtures thereof; X″ is selected from the group consisting of P, As, Sb, Si, Ge, V, and mixtures thereof; Y′ is halogen; 0≦x<3; and 0<y<2; and 0<c≦3;
(iv) Z comprises F, and 0.1<d≦4;
(v) 0<g≦15; and
(vi) wherein M 1 , M 3 , X, Y, Z, a, b, c, d, e, f, g, x and y are selected so as to maintain electroneutrality of said compound.
124. An electrode active material of claim 123 , comprising a material of the formula A a M b (XY 4 ) c Z d having an olivine structure.
125. An electrode active material of claim 124 , comprising a material of the formula A a M b (XY 4 ) c Z d having a NASICON structure.
126. An electrode active material according to claim 123 , wherein A 1 comprises Li.
127. An electrode active material according to claim 123 , wherein M 1 comprises at least one element from Groups 4 to 11 of the Periodic Table, and at least one element from Groups 2, 3, and 12–16 of the Periodic Table.
128. An electrode active material according to claim 127 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.
129. An electrode active material according to claim 128 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Mn, Ti, and mixtures thereof.
130. An electrode active material according to claim 127 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.
131. An electrode active material according to claim 130 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Al, and mixtures thereof.
132. An electrode active material according to claim 123 , wherein X′ comprises Si or a mixture of Si and P, and X″ comprises Si or a mixture of Si and P.
133. An electrode active material according to claim 123 , wherein XY 4 is selected from the group consisting of X′O 4−x Y′ x , X′O 4−y Y′ 2y , X″S 4 , and mixtures thereof, where X′ is P and X″ is P; and 0<x<3; and 0<y<2.
134. An electrode active material according to claim 133 , wherein XY 4 is PO 4−x F x , and 0<x≦0.2.
135. An electrode active material according to claim 123 , comprising particles comprising a material of the formula A 2 e M 3 f O g .
136. An electrode active material according to claim 135 , wherein A 2 comprises Li.
137. An electrode active material according to claim 135 , wherein M 3 is M 4 k M 5 m M 6 n , wherein M 4 is a transition metal selected from the group consisting of Fe, Co, Ni, Cu, Mo, V, Zr, Ti, Cr, and mixtures thereof; M 5 is one or more transition metal from Groups 4 to 11 of the Periodic Table; M 6 is at least one metal selected from Group 2, 12, 13, or 14 of the Periodic Table; and k+m+n=f.
138. An electrode active material according to claim 137 , wherein M 4 is selected from the group consisting of Co, Ni, Mo, V, Ti, Cu and mixtures thereof.
139. An electrode active material according to claim 137 , wherein M 6 is selected from the group consisting of Mg, Ca, Al, and mixtures thereof, and n>0.
140. An electrode active material according to claim 135 , comprising a material of the formula LiNi r Co s M 6 t O 2 , wherein 0<(r+s)≦1, and 0≦t<1.
141. An electrode active material according to claim 135 comprising a material selected from the group consisting of LiNiO 2 , LiCoO 2 , γ-LiV 2 O 5 , Li 2 CuO 2 and mixtures thereof.
142. An electrode active material according to claim 123 , wherein said cubic spinel manganese oxide is Li 1+p Mn 2−p O 4 where 0≦p<0.2.
143. An electrode active material according to claim 123 , additionally comprising a basic compound.
144. An electrode active material according to claim 143 , wherein said basic compound is selected from the group consisting of basic amines, salts of organic acids, and mixtures thereof.
145. An electrode active material according to claim 144 wherein said basic compound is selected from the group consisting of carbonates, metal oxides, hydroxides, phosphates, hydrogen phosphates, dihydrogen phosphates, silicates, aluminates, borates bicarbonates, and mixtures thereof.
146. An electrode active material according to claim 143 , wherein the basic compound is selected from the group consisting of LiOH, Li 2 O, LiAlO 2 , Li 2 SiO 3 , Li 2 CO 3 , Na 2 CO 3 , and CaCO 3 .
147. An electrode active material comprising two or more groups of particles having differing, chemical compositions, wherein
(a) the first group of particles comprises a material of the formula A 1 a M 1 b (PO 4 ) 3 Z d ; and
(b) the second group of particles comprises a material of the formula A 2 e M 2 f O g ;
wherein
(i) A 1 and A 2 are independently selected from the group consisting of Li, Na, K, and mixtures thereof, and 0<a≦8, 0<e≦6;
(ii) M 1 is one or more metals, comprising at least one metal which is capable of undergoing oxidation to a higher valence state, and 0.8≦b≦3;
(iii) M is one or more metals, comprising at least one metal selected from the group consisting of Fe, Co, Ni, Mo, V, Zr, Ti, Mo, and Cr and 1≦f≦6;
(v) Z is OH, halogen, or mixtures thereof, and 0≦d≦6; and
(vi) 0<g≦15; and
(vii) M 1 , M 2 , Z, a, b, d, e, f, and g are selected so as to maintain electroneutrality of said compound.
148. An electrode active material according to claim 147 , wherein A 1 comprises Li.
149. An electrode active material according to claim 147 , wherein M 1 comprises at least one element from Groups 4 to 11 of the Periodic Table, and at least one element from Groups 2, 3, and 12–16 of the Periodic Table.
150. An electrode active material according to claim 147 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof.
151. An electrode active material according to claim 150 , wherein M 1 comprises a transition metal selected from the group consisting of Fe, Co, Mn, Ti, and mixtures thereof.
152. An electrode active material according to claim 147 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof.
153. An electrode active material according to claim 152 , wherein M 1 comprises a metal selected from the group consisting of Mg, Ca, Al, and mixtures thereof.
154. An electrode active material according to claim 147 , comprising particles comprising a material of the formula A 2 e M 3 f O g .
155. An electrode active material according to claim 154 , wherein A 2 comprises Li.
156. An electrode active material according to claim 154 , wherein M 3 is M 4 k M 5 m M 6 n , wherein M 4 is a transition metal selected from the group consisting of Fe, Co, Ni, Cu, Mo, V, Zr, Ti, Cr, and mixtures thereof; M 5 is one or more transition metal from Groups 4 to 11 of the Periodic Table; M 6 is at least one metal selected from Group 2, 12, 13, or 14 of the Periodic Table; and k+m+n=f.
157. An electrode active material according to claim 156 , wherein M 4 is selected from the group consisting of Co, Ni, Mo, V, Ti, Cu and mixtures thereof.
158. An electrode active material according to claim 156 , wherein M 6 is selected from the group consisting of Mg, Ca, Al, and mixtures thereof, and n>0.
159. An electrode active material according to claim 156 , comprising a material of the formula LiNi r Co s M 6 t O 2 , wherein 0<(r+s)≦1, and 0≦t<1.
160. An electrode active material according to claim 147 , comprising a material selected from the group consisting of LiNiO 2 , LiCoO 2 , γ-LiV 2 O 5 , Li 2 CuO 2 and mixtures thereof.
161. An electrode active material according to claim 147 , wherein said cubic spinel manganese oxide is LI 1+p Mn 2−p O 4 where 0≦p<0.2.
162. An electrode active material according to claim 147 , additionally comprising a basic compound.
163. An electrode active material according to claim 162 , wherein said basic compound is selected from the group consisting of basic amines, salts of organic acids, and mixtures thereof.
164. An electrode active material according to claim 162 wherein said basic compound is selected from the group consisting of carbonates, metal oxides, hydroxides, phosphates, hydrogen phosphates, dihydrogen phosphates, silicates, aluminates, borates bicarbonates, and mixtures thereof.
165. An electrode active material according to claim 162 , wherein the basic compound is selected from the group consisting of LiOH, Li 2 O, LiAlO 2 , Li 2 SiO 3 , Li 2 CO 3 , Na 2 CO 3 , and CaCO 3 .Cited by (0)
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